Process for the production of differential effects on polymeric or copolymeric acrylonitrile fibers

ABSTRACT

A process for producing differential effects on polymeric or copolymeric acrylonitrile fibers is provided. The processes carried out by pretreating the fibrous materials with aqueous preparations having a pH-value of between 3 and 5 and containing a colorless cation-active, organic ammonium or sulphonium compound with at least one higher alkyl radical at temperatures of at least 85*C and dyeing the so treated material together with untreated material with at least one cationic dyestuff.

Umted States Patent 1191 111.1 3,869,250 Wegmuller et al. Mar. 4, 1975PROCESS FOR THE PRODUCTION OF 2,922,690 1/1960 Mueller 8/21 ADIFFERENTIAL EFFECTS ON POLYMERIC M i ac e 0R COPOLYMERIC ACRYLOMTRILE3,560,142 2/1971 Keller 8/172 FIBERS 3,643,270 2/1972 Kirschnek 8/l77 AB[75] Inventors: Hans Wegmuller, Riehen; Manfred FOREIGN PATENTS ORAPPLICATIONS Molten P' gasel'Land l,l8l,355 2/1970 Great Britain 8/2l Aboth of Switzerland OTHER PUBLICATIONS [73] Ass1gnee: Clba-Gelgy AG,Basel, Sw1tzerland Beal, American Dyestuff Reporter, June 5, 1967 [22]Filed: June 25, 1973 pages 28-30.

[21] Appl' No; 373292 Primary Examiner-Donald Levy Related US.Application Data Attorney, Agent, or Firm-Wenderoth, Lind & Ponack [63]Continuation-impart of Ser. No l45,58 2, May 20,

I971 abandoned. [57] ABSTRACT A process for producing differentialeffects on polyl l g" Appllcatlon l Data meric or copolym'ericacrylonitrile fibers is provided. May 22, 1970 Switzerland 7573/70 Theprocesses carried out by pretreating the fibrous materials with aqueouspreparations having a pH- [52] US. Cl 8/15, 8/65, 8/169 valueof between3 and 5 and containing a colorless [5 1] Int. Cl D06p 5/12cation-active, organic ammonium 01' sulphonium com- [58] Field of Search8/21, 168 A, 15 pound withat least one higher alkyl radical attemperatures of at least 85C and dyeing the so treated mate- [56]References Cited rial together with untreated material with at least oneUNITED STATES PATENTS callomc dyestuffl 2.746.836 5/1956 Rossin 8/158 7Claims, N0 Drawings PROCESS FOR THE PRODUCTION OF DIFFERENTIAL EFFECTSON POLYMERIC OR COPOLYMERIC ACRYLONITRILE FIBERS CROSS-REFERENCE TORELATED APPLICATION This application is a continuation-in-part of ourpatent application Ser. No. 145,582, now abandoned filed May 20, 197].

The present invention relates to a process for the production ofdifferential effects on fiber material made from polyacrylonitrile orfrom acrylonitrile copolymers, as well as to the fiber material thusdyed in varying shades.

It has already been suggested that resist effects on materials such asfabrics and knitted goods made from hydrophobic fibers, includingpolyacrylonitrile fibers, be produced by the textile material beingtreated in the desired areas with a printing paste containing anaromatic amphoteric compound, and subsequently dye'd. The effectsattainable with such compounds on polyacrylonitrile fiber material haveproved, however, to be inadequate.

It has now been found that effectively differential effects can beproduced, in a simple manner,'on polymeric or copolymeric fibers,wherein said fibers contain at least 80 percent acrylonitrile and havingdyesites corresponding to a color saturation value of at least 1according to the present invention by pretreating saidv fibers with anaqueous preparation, optionally containing thickeners, of a colorless,cation-active, organic ammonium or sulphonium compound containing atleast one higher alkyl radical, i.e., having 8 to 22 carbon atoms attemperatures of at least 85C, preferably 95- 110C, and with a pH-valuebetween 3 and 5, especially between 4 and 4.5; and then dyeing at leastone such pretreated fiber material together with untreated said fibermaterial with at least one cationic dyestuff, wherein the proportion ofthe dyestuff absorbed by the pretreated fibers and the untreated fibersis within 4:96 to 20:80.

Preferably, the pretreatment is carried out with an aqueous preparationcontaining a cation-active organic ammonium compound which contains analkyl radical having 8 to 22 carbon atoms, and of which the cationicpart carries only a single positive charge.

Of particular interest is the use of cation-active organic ammoniumcompounds of the formula:

l min. H

wherein R represents an alkyl radical having 8 to 18 carbon atoms,

R and R" each represent hydrogen, lower alkyl, hydroxy-lower alkyl,lower alkoxy-lower alkyl. cyanolower alkyl; cycloalkyl. or apolyalkylene glycol radical, or

R and R" together with the nitrogen atom binding them representpiperidino or morpholino,

R represents hydrogen, lower alkyl, aralkyl or aralkyl substituted byhydroxyl or lower alkoxy, or

R', R" and R together with the nitrogen atom binding them repesentspyridyl or lower alkylpyridyl,

one of the radicals R", R and R" represents an alkyl radical having 8 to18 carbon atoms, and the others represent hydrogen, alkyl, aralkyl oraralkyl substituted by hydroxyl,

Z represents an alkylene radical having 2 or 3 carbon atoms,

R, R and R" each represent hydrogen, lower alkyl, hydroxy-lower alkyl orlower alkoxy-lower alkyl, cycloalkyl or aralkyl,

Q represents sulphur or -NH-,

r and s represent 1 or 2,

n represents 2 or 3, and

X represents the anion of an organic or inorganic acid.

Good results are obtained, in particular, with a cation-active organicammonium compound of formula Of advantage is, in particular, the use ofcation-active organic ammonium compounds of the formula wherein R, R,R", R' and X have the given meanings.

Of the ammonium and sulphonium compounds to be used, the following 10types of compounds have proved to be particularly interesting: I

1. Compounds of the general formula R, represents an unsubstituted alkylgroup having 8 to 18, preferably 12 to 18, carbon atoms,

R and R each represent, independently of each other, hydrogen, loweralkyl, hydroxy-lower alkyl, lower alkoxy-lower alkyl, cyano-lower alkyl,cycloalkyl, especially cyclohexyl, or a polyglycol ether chain having 2to 40, preferably 5 to 20, alkyleneoxy groups, particularly cthyleneoxygroups, and optionally single propyleneoxy groups or phenylethylcneoxygroups, or

R and R together with the nitrogen atom binding them representpiperidino or morpholino,

R represents hydrogen, lower alkyl, hydroxy-lower alkyl, loweralkoxy-lower alkyl, or aralkyl, espe cially benzyl, and

. X represents the anion of an organic or inorganic acid, such as theanion of formic, acetic, hydrochloric, hydrobromic, sulphuric,phosphoric or methylsulphuric acid.

Examples of suitable compounds of formula (5) are: salts, as defined, ofN-dodecyl-N-cyclohexylamine, N-dodecyl-N-benzylamine, N-cyanoethyl-N-dodecylamine, N,N-bis-(B-hydroxyethyU-N- dodecylamine,N,N-bis-(,B-hydroxyethyl)-N- octadecylamine, N-octadecenyl-piperidine;salts of condensation products of dodecyl, tetradecyl, octadecyl andoctadecenylamine having 2 to 40 moles of alkylene oxide, especiallyethylene oxide, such as salts, as defined, of condensation products ofoctadecylamine having 20 moles of ethylene oxide, or of octadecenylaminehaving moles of propylene oxide. Of the polyethylene oxide additionproducts, those having short ethylene oxide chains are preferred.

Suitable examples of quaternary compounds of formula (5) are:N-dodecyl-N,N,N-trimethylammoniummethosulphate,N-dodecyl-N,N-dimethyl-N- benzylammonium chloride,N-dodecyl-N,N-diethyl-N- B-hydroxyethyl-ammonium chloride, N-tetradecyl-N,N-dimethyl-N-benzylammonium chloride, the reaction product ofoctadecylamine having 10 moles of ethylene oxide, quaternised withdimethyl sulphate, and the reaction product of dodecylamine having 7moles of ethylene oxide, quaternised with epichlorhydrin.

2. Compounds of the general formula:

( ea/Rs R5CONH-(CHa)n-N R1 X wherein R represents unsubstituted alkylhaving 11 to 17 carbon atoms,

R and R each represent an unsubstituted lower alkyl group, and

n represents 2 or 3, and

R and X have the given meanings.

Examples of suitable compounds of formula (6) are salts, as defined, ofcompounds obtained by condensation of coconut oil fatty acid chloridewith N,N- dimethylpropylenediamine, as well as the salts of quaternarycompounds obtainable from the said condensation products by reactionwith dimethyl sulphate, glycol chlorohydrin, epichlorohydrin, or benzylchloride.

3. Compounds of the general formula:

wherein R,, represents unsubstituted alkyl having 8 to 18 carbon atomsor an alkyl chain, interrupted by oxygen atoms, having 8 to 18,preferably 12 to 18, carbon atoms, and R represents hydrogen, the methylgroup or ethyl group, and

5 X has the given meaning.

Examples of suitable compounds of formula (7) are: dodecyl-pyridiniumchloride, octadecyl-pyridinium chloride, dodecyl-3- or-4-methylpyridinium chloride and octadecyloxymethylpyridinium chloride.4. Compounds of the general formula wherein of R and R one represents anunsubstituted alkyl group having I] to 18 carbon atoms, and the other Rrepresents hydrogen or a lower alkyl radical optionally substituted byhydroxyl groups,

R represents hydrogen and if R or R donot represent hydrogen also alower alkyl radical optionally substituted by hydroxyl groups, or itrepresents an aralkyl radical, especially the benzyl radical, and

n represents 2 or 3, and

X has the given meaning.

Examples of suitable compounds of formula (8) are:Z-heptadecyl-imidazolinium-acetate, l-B-hydroxyethyl-2-heptadecyl-imidazolinium chloride, 1-B-hydroxyethyl-2-heptadecyl-3-methylimidazoliniummethosulphate,l-undecyl-2-methyl-imidazolinium chloride, andZ-heptadecenyl-tetrahydropyrimidinium chloride.

5. Compounds of the formula wherein R represents an unsubstituted alkylgroup having 12 to 18 carbon atoms, R represents hydrogen, anunsubstituted alkyl group having up to 18, preferably 1 to 4,carbonatoms, or the unsubstituted phenyl radical, R represents anunsubstituted lower alkyl group, or

the benzyl radical, and X represents the anion of hydrochloric orhydrobromic acid, or of methylsulphuric acid. Mentioned as examples ofcompounds of formula (9) are: l-dodecyl-3-benzyl-imidazolium chlorideand lhexadecyl-2-isopropyl-3-methylimidazoliummethosulphate.

R represents an unsubstituted alkyl group having 1 l to 17 carbon atoms,and

R R and R each represent, independently of each other, hydrogen, a loweralkyl radical optionally substituted by hydroxyl or lower alkoxy groups;a cycloalkyl or an aralkyl group, especially the cyclohexyl or benzylradical, and

X has the given meaning.

Examples of suitable compounds of formula l l) are:heptadecenyl-amidinium chloride, undecyl-N-benzylamidinium chloride,heptadecyl-N,N,N'-trimethylamidinium-methosulphate and heptadecyl-N-B-methoxypropyl-amidinium chloride.

7. Compounds of the formula Ll. is.

wherein R represents a lower alkyl radical optionally substituted byhydroxyl groups, especially the methyl radical, or a polyglycol etherchain having 2 to 40, preferably 5 to 20 alkyleneoxy groups,particularly ethyleneoxy groups, and optionally single propyleneoxygroups or phenylethyleneoxy groups,

n represents 2 or 3, and

m represents a whole number from 1 to 4, and

R R, and X have the given meanings.

Examples of suitable compounds of formula l 2) are: salts, as defined,of N-substituted derivatives of dodecyl-, tetradecyl-, octadecyl-,octadecenyl-ethylenetriamine, -propylenediamine, -diethylenetriamine,-dipropylenetriamine and -tetraethylenepentamine, such asdichlorohydrate of N-dodecyl-N-methyl-N,N'- dimethylpropylenediamine, oran addition product quaternised with dimethyl sulphate of to molesofethylene oxide with N-octadecyl-diethylenetriamine.

8. Compounds of the formula wherein R represents an unsubstituted alkylgroup having 8 lo 18', preferably l2 to 18, carbon atoms, and R and Reach represent, independently of each other, hydrogen, or a lower alkylradical optionally substituted by hydroxyl or lower alkoxy groups,whereby R and R together with the group can also form the radical of apartially saturated ring, particularly ofa diazoline ortetrahydrodiazine ring, and

X has the given meaning.

Mentioned as examples of suitable compounds of formula (12) are:N-octadecyl-guanidinium chloride, N- 5hexadecyl-N-methyl-N"-B-hydroxyethyl-guanidinium chloride,and2-octylamino-imidazolinium acetate.

9. Compounds of the formula (13) N-R24 6B ai-s o 1 11 wherein Rrepresents an unsubstituted alkyl group having 8 to 18, preferably 12 tol8, carbon atoms, and

R R and R each represent, independently of each other, a lower alkylradical optionally substituted by hydroxyl or lower alkoxy groups; acycloalkyl or aralkyl radical, especially the cyclohexyl or benzylradical, or

R and R together withthe group form the radical ofa partially saturatedring, particularly of a diazoline or tetrahydrodiazine ring, and

- /R2a G9 R1S cm s 04 wherein R, represents an unsubstituted alkyl grouphaving 8 to 18, preferably II! to 18, carbon atoms, and

R and R each represent a lower alkyl radical optionally substituted byhydroxyl groups.

An example of such a compound is: S-dodecyl-S-methyl-S-B-hydroxyethyl-sulphoniummethosulphate.

In the foregoing, the term lower in connection with alkyl or alkoxygroups denotes, as a rule, a radical having not more than 4 carbonatoms. By higher alkyl radicals are meant, as a rule, radicals havingabout 8 to 22 carbon atoms. In the process according to the invention itis possible to use mixtures of the cation-active compounds. Of thecompounds of formulae to 14, those of formula 5 are especiallypreferred.

The cation-active compounds, as defined, are advantageously used inamounts of at least l per cent by weight, especially 2 to per cent byweight, relative to the weight of the fiber material to be treated.

The aqueous preparation usable in the process according to the inventionoptionally contains the usual thickeners for the printing of fibermaterial made from polyacrylonitrile, or acrylonitrile copolymers, suchas solubilised types of rubber, e.g. that known as crystal rubber," orthickeners with a cellulose base, such as 10- cust bean flour,galactomannans, tragacanth, British gum, polysaccharides, or cellulosederivatives such as methyl cellulose, or soluble salts of carboxymethylcellulose. Preferred are thickeners made from locust bean flour andgalactomannans.

For the purpose of adjusting to the desired pH-value, it is possible toadd to the aqueous preparation usable according to the invention theusual auxiliaries, especially organic acids such as formic or aceticacid, buffer substances such as ammonium salts or alkali metal salts,e.g. ammonium, sodium or potassium acetate, -propionate or -eitrate, aswell as, optionally, neutral salts such as sodium sulphate or sodiumchloride.

As fiber material made from polyacrylonitrile or from acrylonitrilecopolymers the commercially known types of fibers can be used. In thecase of acrylonitrile copolymers, the proportion of acrylonitrile shouldbe advantageously at least 35 per cent by weight and preferably at least80 per cent by weight of the copolymer. Furthermore. they possesssufficient dyesites to impart to the fibers a color saturation value ofat least 1 and especially in the range of about 1.1 to 3.5. Suitablecomonomers include other vinyl compounds, e.g. vinylidene chloride,vinylidene cyanide, vinyl chloride, methacrylate. methylvinylpyridine,N- vinylpyrrolidone, vinylacetate, vinyl alcohol, or styrenesulphonicacids.

The acid groups of copolymer effecting the affinity of the dyestuff aremainly the carboxylic acid, carboxylic acid amide or hydroxy groups aswell as the sulfonic acid group.

The balance is essentially derived from vinylpyridines and othermonomers copolymerizable with acrylonitrile which are decribed, forinstance, in Canadian Pat. No. 557,597, issued May 20, 1958.

Suitable acrylic fibers which satisfy the above requirements areproduced from spinnable solutions described for instance in British Pat.No. 830,830, published Mar. 23, 1960, and German Pat. No. 1,075,317,published Feb. 11, 1960.

Commercially available fibers of the above-described type are, forinstance, Acrilan 16, Orlon 42 and Dralon.

This fiber material can be pretreated and/or dyed in any stage ofprocessing, e.g. it can be in the form of loose material, rovings, yarnsor knitted goods, such as knitted fabrics, fabrics or fiber fleecematerials, as well as textile floor coverings such as woven, tufted, orfelted carpets.

As cationic dyestuffs for the dyeing of the fiber material pretreatedaccording to the invention and made from polyacrylonitrile oracrylonitrile copolymers. together with untreated acrylonitrile polymersfiber material, can be used the usual such compounds, generallychromophorous systems the cationic character of which comes from anonium group such as a carbenium, ammonium, cyclammonium. oxonium, orsulphonium grouping, and which are in the form of watersoluble salts.These dyestuffs have advantageously a saturation value of 0.15 to 2,especially 0.18 to 1. Examples of cationic dyestuffs containing suchchromophorous systems are: acrylazo, anthraquinone, methine, azamethine,azine, oxazine, thiazine, xanthene, acridine, polyarylmethane andcoumarin dyestuffs.

Fibre material made from polyacrylonitrile or acrylonitrile copolymerpretreated according to the invention can, optionally, be processed anddyed (with application of suitable dyestuffs having affinity to fibres)not only together with untreated acrylonitrile polymer fibre materia,but also with other untreated fibre material. Suitable for this purposeare, in particular, fibre materials made from linear high-molecularesters of aromatic polycarboxylic acids with polyfunctional alcohols,such as polyethylene glycol terephthalate fibres, and syntheticpolyamide fibre material, as well as the corresponding acid modifiedfibres. Particularly interesting multi-colour effects are obtained, forexample, by the dyeing of fibre mixtures made up of pretreatedpolyacrylonitrile fibres, untreated polyacrylonitrile fibres, andnonmodifted polyester fibres or synthetic polyamide fibres using acombination of the above mentioned cationic dyestuffs and the usualdispersion dyestuffs. The dyeing of such fibre mixtures may also becarried out by dyeing first with dispersion dyestuffs and afterwardswith cationic dyestuffs. Such dispersion dyestuffs can belong to anydesired classes of dyestuffs; thereby suitable are, in particular, azodyestuffs, or also anthraquinone, nitro, methine, styryl, azastyryl,naphthoperinone, quinophthalone, or naphthoquinoneimine dyestuffs.

The pretreatment of the fibre material made from polyacrylonitrile oracrylonitrile copolymers with the aqueous preparation (optionallycontaining thickeners) of a cation-active compound as defined above canbe carried out by methods common for the dyeing or printing ofacrylonitrile fibre material, that is, for example, by the so-calledexhaust process in a long liquor (ratio of goods to liquor ca. 1:10 to1:50), optionally under pressure, at temperatures between C and about110C, preferably to C, for 30 to 180 minutes; by impregnation,particularly by padding, e.g. in the form of slubbing, at temperaturesbelow 80C, especially at 30 to 40C, and subsequent heat treatment suchas steaming, preferably using neutral saturated steam, and optionallyunder pressure, at temperatures of, for example, 98to C for 3 to 30minutes; or, finally, also by printing, such as by roller printing, andsubsequent steaming, preferably under pressure at temperatures of ca.105 to 140C for 3 to 30 minutes.

It was most surprising to obtain the high differential effect merely bytreating one portion of the fibers by the process according to theinvention. The untreated fibers take up much as 80 to 96 percent of thetotal absorbed dyestuff whereas the treated fibers only take up theremaining 4 to percent.

This magnitude of differential effect could not be expected from aconsideration of the prior art because under extended dyeing conditions,the prior art ammonium compounds do not block the fiber permanently andenable level dyeings on acrylic fibers. Such compensation is one of theprerequisites of a leveler.

By contrast the ammonium compounds employed according to the inventionpermit retention of a strong blockage over extended dyeing periods.Consequently, also by a prolongation of the dyeing duration theproportion of the differential effects obtained according to theinvention remains unchanged.

The fiber material pretreated in such a manner is subsequentlyadvantageously rinsed both with warm and with cold water, and thendried; the said fibre material is then dyed together with untreatedfibre material made from polyacrylonitrile or acrylonitrile copolymers,in a manner known per se, with at least one cationic dyestuff.Preferably, the dyeing is performed from an aqueous liquor by theexhaust process (ratio of goods to liquor ca. 1:10 to 1:50), attemperatures of ca. 85 to 110C, with the addition of the usual dyeingauxiliaries, such as organic acids, particularly acetic acid, for thepurpose of adjusting the pH-value of the dye liquor to between 3.5 and5. The fibre material can, however. also be dyed continuously, i.e., byimpregnation with a thickened dye liquor containing standard dyeingauxiliaries, such as dye carriers and acid, and subsequent heattreatment, especially steaming at temperatures of ca. 98 to 105C.

Depending on the nature of the pretreatment and combination of fibermaterial made from polyacrylonitrile or acrylonitrile copolymerspretreated according to the'invention with untreated fiber material madefrom polyacrylonitrile or acrylonitrile copolymers, as well as,optionally, with other untreated fiber material, very effective twoandmulti-shade effects can be obtained. Fiber material pretreated accordingto the invention can be stored as desired and processed at any time, anddyed in the desired shades, thus the expensive storage of large amountsof pre-dyed material can be avoided. The process according to theinvention also renders possible the dyeing, in a simple manner, of fibermaterial of the same quality in varying shades, an aspect which,especially in the case of the manufacture of carpets, is of greatimportance, since carpets can thereby be produced which, with respect tostability and lustre of the nap, present a uniform and harmoniousappearance.

The color saturation value of the acrylic fibers mentioned in thisspecification is the constant saturation value of usable acrylic fiberswith a basic dye-stuff of average affinity, for example, malachite greenfor such fibers, expressed in grams of dyestuff per 100 grams of fiber.

The saturation value" of the dyestuff mentioned in this specificationcorresponds to the quotient from the saturation value ofthe fiber andthe saturation concentration value of the dyestuffs. This latter valuerepresents the amount of the dyestuff absorbed by the fiber whensaturation point is attained. The saturation concentration value of thedyestuff is given in grams pro 100 grams of fiber.

The temperatures are given in degrees Centigrade in the followingexamples.

EXAMPLE 1 An amount of 50 g of polyacrylonitrile yarn, e.g. Orlon 42yarn, is introduced into a pretreatment bath containing 2.5 g ofoctadecylamine acetate, 2 ml of 40 percent acetic acid, and l g ofsodium acetate dissolved in 1,000 ml of water. The temperature ofthe dyeliquor is raised, with continuous movement of the textile ma terial,within about 30 minutes up to the boiling point, and boiling is thenmaintained for 90 minutes. The treated polyacrylonitrile yarn isafterwards rinsed with warm water and then dried.

The thus pretreated 50 g of polyacrylonitrile yarn are processedtogether with 50 g of untreated polyacrylonitrile yarn on a knittingmachine to produce a knitted fabric.

The knitted material pretreated in this manner is now dyed for minutesat boiling temperature in a fresh bath containing, in 2,000 ml ofwater,1.25 g ofthe dyestuff of the formula cmorno 1r ZnClz 4 ml of 40 percentacetic acid, and 10 g of crystallised sodium sulphate. The dyed materialis subsequently rinsed with lukewarm water and then with cold water, andafterwards dried.

In this manner a knitted fabric displaying a clear light-blue/dark-bluetwo-shade effect is obtained. By means of reflection measurement thefollowing color distribution was established. The polyacrylonitrile yarnpart, pretreated according to the present invention, had taken up 8percent of the total absorbed dyestuff; and the untreatedpolyacrylonitrile yarn part 92 percent of the absorbed dyestuff.

lf, in the above example, the 2.5 g of octadecylamine acetate arereplaced by the stated amounts (shown in the second column of thefollowing Table 1) of the pretreatment agents listed in the thirdcolumn, the pretreatment and the dyeing being then carried out under theconditions described in Example 1, then similar light-blue/dark-blueeffects are obtained on the knitted fabric. The proportions of dyestuffabsorbed by the pretreated fibres and by the untreated fibres are givenin Columns 4 and 5.

TABLE 1 Absorbed dyestuff in percent lretreuted Untreatedpolyacrylopolyacrylo- Amount nitrlle nitrlle Example N 0. in g.Pretreatment agent; yarn yarn b TABLE lContinuecl Absorbed d estutl' inpercent Pretreated Uni rented polyacrylopol \'acr \'lo F l f fl nitrilenilrilc p c l t Pretreatment agent yarn yarn sun t i ..t.. 2.5 C|7|H372U U CH3-IT'-(CH:CHQO)XIH l 3 SOlCHs" 5 CH3-"III (CH2C1'I20) H (IIJH CH(CIIQCI'IQO)KQII CII -N (omomomn I1+12+$3+9fl=20 C11 aa H CHzCOO'CHzCHzOH C1- (1H2 CH O CH2 EXAMPLE 6 2 g of the dyestuff of the formulaAn amount of 1 kg of polyacrylonitrile flock (Orlon 42) is introducedinto a dyeing apparatus. A dye liquor is prepared separately containing,dissolved in 15 litres of water, 30 g of octadecylpyridinium chloride 40ml of 40 percent acetic acid, and g of sodium acetate. This pretreatmentdye liquor is then pumped into the dyeing apparatus; the temperature ofthe dye liquor is subsequently raised, within ca. 20 minutes, up to theboiling point, and boiling is maintained for 90 minutes. The pretreatedpolyacrylonitrile flock is afterwards rinsed with warm water,centrifuged, dried, and then spun to obtain a carpet yarn. The thusobtained carpet yarn having low affinity to cationic dyestuffs issubsequently processed together with 1 kg of untreated polyacrylonitrileyarn ofthe same quality, on a tufting machine, into a carpet.

A piece weighing 1 kg of this carpet is then fed into a winch vat andstitched at the ends. On to the material to be dyed are poured ca.litres of water at and 100 g of crystallised sodium sulphate are added.Separately, in ca. 4 litres of water containing 40 ml of 40 percentacetic acid, are dissolved 10 g of the dyestuff of the formula and 1.5 gof the dyestuff of the formula The obtained dyestuff solution isthereupon carefully added to the dye liquor. The temperature of the dyeliquor is then raised within 45 minutes to and dyeing. carried out for60 minutes with slight boiling of the dye liquor. The dyed carpet isfirst rinsed with warm water and afterwards with cold water, and dried.In this manner is obtained a carpet having a light-brown and dark brownpattern.

By means of reflection measurements was determined the following colourdistribution: Drawn on to the untreated polyacrylonitrile yarn part was4% of the total absorbed dyestuff, and on to the untreatedpolyacrylonitrile yarn part 96 percent of the total absorbed dyestuff.

as omo- 211013 cr-ncmou Similar effects are obtained by using instead ofOrlon 42 flock, with otherwise the same procedure, polyacrylonitrileflock made from Acrilan, Crilenka, Dralon, or Exlan.

EXAMPLE 7 If, in the preceding Example 6, the 30 g ofoctadecylpyridinium chloride are replaced by 50 g of the pretreatmentagent according to Example 3, the pretreatment being otherwise carriedout as described in Example 6, and the carpet obtained by processing ofthe treated and untreated fibre material is then dyed under theconditions given in Example 6, whereby is used, however, instead of thedyestuff combination mentioned in the preceding example, a dyestuffmixture 1 consisting of 6 g of the dyestuff of the formula and 6 g ofthe dyestuff of the formula CI'IZCHI O H then is obtained a carpet dyedlight-green/dark green. The reflection measurements gave the followingvalues; Absorbed on the pretreated fibre part is l9 percent, on theuntreated part 81 percent ofthe total absorbed dye stuff.

EXAMPLE 8 If in Example 6 are used, instead of the 30 g ofoctadecylpyridinium chloride, 50 g of the pretreatment agent of theformula the pretreatment being carried out as described in Example 6.and the polyacrylonitrile fibre material which has been processed in thesame manner into a carpet then dyed, under the dyeing conditions givenin Example 6, with a dyestuff mixture consisting of 4 g of the dyestuffof the formula and 8 g of the dyestuff of the formula N if AL /orn /N=NNcmsm our CH:

then is obtained a carpet made up a. of untreated polyacrylonitrile yarndyed an intense scarlet red, and

b. of pretreated polyacrylonitrile yarn dyed slightly yellowish red. Theratio of the amount of dyestuff absorbed by the treatedpolyacrylonitrile fibre material to the amount absorbed by the untreatedpolyacrylonitrile material is 20 80.

EXAMPLE 9 If the pretreatment of the polyacrylonitrile flock is carriedout as described in Example 6, using, however, 50 g of thequaternisation product of N-dodecyl-N,N- dimethylamine withepichlorhydrin instead of the 50 g of octadecylpyridinium chloride usedin Example 6, and the fibre material is processed in the same mannerinto a carpet, the said fibre material consisting of iden tical parts ofpretreated material and untreated material, and dyed, under the dyeingconditions described in Example 6, with 5 g of the dyestuff of theformula l Zn on EXAMPLE 10 A printing paste containing 50 g/l of thepretreatment agent of the formula 5 g/l of locust bean flour thickener,and 5 ml/l of percent acetic acid is applied, with the aid of a rollerprinting machine, to a fabric made from polyacrylonitrile fibres. Theliquor applied amounts to ca. percent printing paste, relative to thedry weight of the fab- The fabric printed with the pretreatment agent isafterwards steamed for 15 minutes at a temperature of and at 1atmosphere, whereupon the steamed material is rinsed with warm water andthen dried.

A piece of this pretreated polyacrylonitrile fibre fabric weighing 1 kgis then fed into a winch vat and stitched at the ends. Into the winchvat are then poured 35 litres of water at ca. 40, and 100 g ofcrystallised sodium sulphate are added.

To about 3 litres of water are added, in a separate operation, 40 ml of40 percent acetic acid, whereupon are added 10 g of the dyestuff of theformula of the formula [Cl2H25-'N 1 Cl CzHs are replaced by theidentical amount of one of the pre-' treatment agents listed in thefollowing Table II, in the second column, the procedure for thepretreatment and for the subsequent dyeing being as described in Example10, then likewise are obtained colour printings having a slightlyred/intense red pattern.

CHzCH-O(CH2CII20): H Hz 2 Table ll Continued Example N0. Pretreatment;agent 16 /CII2CIIQCN Cia asN CIIQCIIQOII Bl CIIgC lIg-O CH3Cl1II23CONII(C1I2)3 N CH CH2 18 C13II35OCII CII CII N(CIIflaFCIIaSOF 19/C2I'I5 l Ci7H CONII(CHz)zN\ 11 Cl v CzHsJ C1r a1 i\ C1 7 O18H35' O CH2N \l Cl 22 CI a N-CH2 Cr7H35-C CHgSOF NCH OIIQCHZOH 23 N-CH C1rH2aC\01 whom-I 5 CH3 24 NCH l*' Ci1 aa-O OH; H 01- NH-CH2 25 NCH2 CHa-C\ H BIIF- HZ-I CIH IIH NCH CH -C l CHaS O N-CH2 --(]]II /NCgz CH3C\ /CH2 Cl-N-CH2 lizHzs 28 ([JHz- /NCII s l III-CH Table II Continued If in Example1 is used, instead of the 2.5 g of octadecylamine acetate, the sameamount of the pretreat- Example Pretreatment agent ment agent stated inthe preceding Examples to 43, 29 CH3 the pretreatment being carried outas described in Ex- I 5 ample l, and the knitted fabric which has beenpro- H3 NOH duced 1n an analogous manner then dyed under the OH O\OHaSOF conditions given in Example I, then a knitted fabric is CH; IIICHobtained displaying a similarly good light-blue/dark 0 m, blue two-shadeeffect.

30 EXAMPLE 44 Ci1Haa-C -H Cl- J Into a pretreatment bath containing 1.5g of the pre NHz treatment agent of the formula 31 NH T C11HzzC --H 01-15 (m) [c H 1\r 1 (31 NIL-CHPQJ r r 2 ml of 40 percent acetic acid and lg of sodium acetate 33 N-CHa T dissolved in 1,200 ml of water areintroduced 50 g of Ci7Ha5C CH3 H CHBSOF polyacrylonitrile yarn. Withcontinuous movement of N the textile material, the dye liquortemperature is then raised withinn ca. minutes to 95, and boiling issub- 33 NH sequently maintained for 90 minutes. The treatedpolyacrylonitrile yarn is afterwards rinsed with warm water CIYHKPC Tand then dried.

NH(OH2)3OCH3 25 An amount of 50 g of untreated polyacrylonitrile 34 CH3CH3 yarn is then combined with the polyacrylonitrile yarn C H l CH l CH2 CH pretreated in the above descr1bed manner and pro- W 2 2 3 3 4cessed on a knitting machine into a tricot.

In a fresh bath containing, dissolved in 2,000 ml of 35 omomon CHZCHZOHH 30 water, 0.5 g of the dyestuff of the formula C17II35NCI{3CII2CI12N\2 C1 (115) Hz i CI'IQCHQOH Cl e CH3 C2115 CH1CHzN(CH3)2 or (CHzCH20)xH(CHzCH2O); H oH2oH20)X HH C171I35NCH2CH2 -CH2CH2-N H 3 Cl- (0 H2 0112O) El-TH: 1+ s-i- 4= I C Ha1NIIC H (31- 4 ml of percent acetic acid and10 g of sodium sul- I phate is then dyed the knitted fabric for 60minutes at 38 N CH boiling temperature. The dyed material is afterwardsT a rinsed with warm water and then with cold, and finally C1sI-Ia3-NH-C--H Cl d i d NH-CHzCHzOHJ 39 z"l In this manner is obtained a knittedfabric presenting oa1rtTNrI-o H omoooa slightly yellow brown/intenselyyellow brown two- NIPOHQJ shade effect. By means of reflectionmeasurements, the 40 0 NH t, following colour distribution wasdetermined: The i polyacrylonitrile yarn part pretreated in thedescribed Crz'llz5-SC -H 01 J manner has absorbed 9 percent of the totalabsorbed dyestuff, and the untreated part 91 percent of the total 41 NHT absorbed dyestuff.

C12H25S-C H o1 QJ If polyacrylonitrile yarn is pretreated according to42 NH the information given in Example 44, and combined 0 U S C i H Cwith untreated polyacrylonitrile yarn; and if is used for 2P 1 thedyeing of the finished knitted fabric, instead of the n 0.5 g of thedyestuff mentioned in the preceding Example 44, in each case 1 g of oneof the dyestuffs listed in '13 Column 2 of the following Table [I], thenis obtained knitted fabric dyed in the shades given in Columns 3 and 4.

TABLE III Shade on polyaerylonitrile yarn Example N0. DyestufiPretreated Untreated 45 C2115 Slightly bluish lntensely bluish red. red.OzN- N=N N OzII4O-N(CH;O: c1-

46 /C 2H5 Slilghtly yellow lnltgensely yellow CzII4-N Cl" 47 (H)IIIH-CHg Slightly blue. Intensoly blue.

OH SOr Y 0 2)a a)a 48 OH; Slightly pink. Intensely pink.

C Ha C2H5 \N/ CH=CHN znclr I 02115 49 0 H3 Slightly yellow. Intenselyyellow.

- CHa CH=CHNHO CH3 cmsor I C H 50 01 I Light-brown. Dark-brown-C2H5N(CH3)3 C1- C1 51 ([JH $H; Light-blue. Intensely blue.

HzN- L NHz HaC CH3 Cl- EXAM PLE 52 The thus produced knitted article isthen fed into a In a closed laboratory dyeing apparatus are placed 300 gof polyacrylonitirle yarn in the form ofa cheese. A pretreatment liquoris prepared separately containing, in 4.5 litres of water, g of thepretreatment agent of the formula 0 1133 C O NH (CH2) 3N (CH3) 2-H Cl 12ml. of 40 percent acetic acid, and 6 g of sodium acetate. Thispretreatment liquor is then transferred to the dyeing apparatus; thetemperature is raised within ca. minutes to 105- 107, and thistemperature is maintained for 90 minutes. The pretreatment liquor isafterwards cooled to room temperature, the dyed material rinsed withwarm water, centrifuged, and then dried.

The thus pretreated polyacrylonitrile yarn is then combined with 500 gof untreated polyacrylonitrile yarn and with 500 g of yarn made frompolyethylene glycol terephthalate, and the whole processed, on aknitting machine, into a knitted article.

winch vat. An amount of ca. 40 litres of water is poured in, and asswelling agent are added g of an emulsion of the sodium salt ofo-phenylphenol, as well as 80 g of diammonium sulphate. With continualmovement of the textile material, the temperature of the dye bath israised within 15 mintues to about 60.

in a separate operation 26 g of a dyestuff preparation containing, infinely dispersed form, the dyestuff of the formula Q orno- -N=N-C co aresuspended in ca. 500 ml of water. The obtained dyestuff dispersion isthen carefully added to the dye liquor, whereupon the temperature of theliquor is raised, within ca. 30 minutes, from 60 to 95. Dyeing issubsequently carried out for minutes with gentle boiling. The dyedmaterial is rinsed with hot water, then soaped, and again rinsed withwater.

The cross-dyeing of the treated and the untreated polyacrylonitrile yarnpart is performed as follows:

Into the winch vat are again placed 40 litres of water at ca. 40, and tothis are added 100 g of crystallised sodium sulphate. In ca. litres ofwater containing 32 ml of 40 percent acetic acid are dissolved, in aseparate operation, g of the dyestuff of the formula The obtaineddyestuff solution is now carefully added to the dye liquor. Thetemperature of the liquor is thereupon raised within 1 hour to 95, anddyeing is subsequently carried out for 60 minutes with gentle boiling;the knitted article is thereupon rinsed with warm water, centrifuged,and finally dried. with observance of the above conditions is obtained aknitted article which is made up of a. polyethylene glycol terephthalateyarn dyed greenish yellow,

b. pretreated polyacrylonitrile yarn dyed light-green,

and

c. untreated polyacrylonitrile yarn dyed an intense bluish green.

We claim:

1. Process for the production of differential effects on copolymericacrylonitrile fibers, wherein said fibers containing at least 80 percentby weight of acrylonitrile a) are treated at temperatures of at least85C with a pH-value of between 3 and 5, with an aqueous perparationconsisting essentially of at least one cation active organic ammoniumcompound of the formula:

R represents an alkyl radical having 8 to 18 carbon atoms,

R and R" each represent hydrogen, lower alkyl, hydroxy-lower alkyl,lower alkoxy-lower alkyl, cyanolower alkyl, cycloalkyl, or apolyalkylene glycol radical, or

R and R" together with the nitrogen atom binding them representpiperidino or morpholino,

R' represents hydrogen, lower alkyl, aralkyl, or aralkyl substituted byhydroxyl or lower alkoxy, or

R, R" and R together with the nitrogen atom binding them representpyridyl or lower alkylpyridyl,

r represents 1 or 2,

n represents 2 or 3, and

x represents the anion of an organic or inorganic acid,

and b) said acrylic fibers, treated according to a), are dyed togetherwith untreated material made from said acrylic fibers in a dyehathconsisting essentially of an aqueous liquor with at least one cationicdyestuff, wherein the proportion of the dyestuff absorbed by the fiberspretreated according to a) and by the untreated fibers is within 4:96 to20:80.

2. Process according to claim 1, wherein the treatment a) is carried outwith an aqueous preparation containing, as cation-active organicammonium compound, a compound of the formula:

wherein R, R, R", R' and X have the meanings given in claim 1.

3. Process according to claim 2, wherein the cationactive ammoniumcompound has the formula:

wherein R represents hydrogen, lower alkyl, hydroxy-lower alkyl, loweralkoxy-lower alkyl or aralkyl, R represents unsubstituted alkyl having 1l to 17 carbon atoms,

n represents 2 or 3, and

X represents the anion of an organic or acid. 5. Process according toclaim 1, wherein the cationactive ammonium compound has the formula:

inorganic wherein R represents unsubstituted alkyl having 8 to 18 carbonatoms or an alkyl chain interrupted by oxygen atoms, having 8 to 18carbon atoms,

R represents hydrogen, methyl or ethyl, and

X represents the anion of an organic or inorganic acid.

6. Process according to claim 1, wherein the cationactive ammoniumcompound is octadecylamine ac- 65 etate.

7. The fiber material made from polyacrylonitrile or from acrylonitrilecopolymers, dyed according to claim 1 in differential shades.

R and R each represent unsubstituted lower alkyl,

1. PROCESS FOR THE PRODUCTION OF DIFFERENTIAL EFFECTS ON COPOLYMERICACRYLONITRILE FIBERS, WHEREIN SAID FIBERS CONTAINING AT LEAST 80 PERCENTBY WEIGHT OF ACRYLONITRILE A) ARE TREATED AT TEMPERATURE OF AT LEAST85*C. WITH A PH-VALUE OF BETWEEN 3 AND 5, WITH AN AQUEOUS PERPARATIONCONSISTING ESSENTISLLY OF AT LEAST ONE CATION ACTIVE ORGANIC AMMONIUMCOMPOUND OF THE FORMULA:
 2. Process according to claim 1, wherein thetreatment a) is carried out with an aqueous preparation containing, ascation-active organic ammonium compound, a compound of the formula: 3.Process according to claim 2, wherein the cation-active ammoniumcompound has the formula:
 4. Process according to claim 1, wherein thecationactive ammonium compound has the formula
 5. Process according toclaim 1, wherein the cationactive ammonium compound has the formula: 6.Process according to claim 1, wherein the cationactive ammonium compoundis octadecylamine acetate.
 7. The fiber material made frompolyacrylonitrile or from acrylonitrile copolymers, dyed according toclaim 1 in differential shades.